Hydantoin produced polyurethane

ABSTRACT

A polyurethane prepared by reacting a mol of a reactive hydrogen material of 700 and higher molecular weight with 1.2 to 3.5 mols of organic polyisocyanate and 0.2 to 2 mols of dihydroxyalkyl dialkyl hydantoin where the alkyl radical contains from 1 to 10 carbon atoms.

United States Patent 1191 Reilly et al. E Dec. 23, 1975 HYDANTOIN PRODUCE) POLYURETHANE 2,995,530 8/1961 Frisch et al. 260/77.5 AQ 3.365.426 1/l968 Wallea 260/715 A0 [75] 3,635,845 1/1972 Porret =1 al 260/2 N 32:" M 05 3,681,282 8/l972 Preston 260/465 15 [73] Assignee: The Goodyear Tire & Rubber Primary Examiner-M. J. Welsh my Akron. Ohlo Attorney, Agent, or Firm-F. W. Brunner; J. D. Wolfe [22) Filed: Dec. 26, 1973 [2]] App]. No.: 428,594 [57] ABSTRACT A polyurethane prepared by reacting :1 mol of a reac- {521 Us 2450/75 Q; A0 tive hydrogen material of 700 and higher molecular [51] Int. Cl. C08G 18/38 weight with L2 to 3.5 mols of organic polyisocyanate field of Search.. 260/775 A0. 2.5 A0, 75 NO and 0.2 to 2 mols of dihydroxyalkyl dialkyl hydantoin where the alkyl radical contains from 1 to 10 carbon [56] References Cited atoms.

UNITED STATES PATENTS 2,850,474 9/1958 Maxey 260/75 N0 3 Claims No Drawings HYDANTOIN PRODUCED POLYURETHANE This invention relates to a method of making im- EXAMPLE u The experiment of Example I was repeated except 372.3 parts of H MDl was used and the physical propproved polyurethanes and to said polyurethanes. More 5 erties of this polyurethane are Sho in Table particularly, this invention relates to thermoplastic Table [I polyurethanes which may be solvent soluble.

The polyurethanes of this invention can be made by Pmpcm using the one-shot, prepolymer or quasi prepolymer Modulus I! v 1 i lU BOW/r Modulus. psl (1| l5 methods to react a reactive hydrogen material with an Ummuw mum psi organic polyisocyanate and a curative of di-hydroxyal- Ultimate Elongation, 328 kyl alkyl hydantoin to give a cured polyurethane. Use Viscmlty' of the dihydroxalkyl alkyl hydantoins where the alkyl group has from 1 to H) and preferably 1 to 5 carbon l S atoms and higher result in the polyurethanes having EXAMPLE [[1 improved hardness and modulus. Where the alkyl, alkyl I radical substituent on the dihydroxy alkyl, alkyl hydan- The polyurethane comPol-mds were Pr toin is hydroxyl ethyl, methyl. it gives with the reaction PYOFedU'e dcscnbefl m Example I with followproduct of an aliphatic or alicyclic polyisocyanate and mg reclpes (If Table a polyester polyol or polyether polyol, preferably the Table III polyol that is a diol or trio], a nonlight-cliscoloring poly- 3A 3B urethane. For instance, where the alicyclic polyisocyanate is a fully hydrogenated methylene-di-phenyl isocymm anate, hereinafter H MDI, the polyurethane is a non- Diglycolamine (DOA) 7.35 7.35 discoloring thermoplastic having improved melting gg'g point and thermal stability. Also, the thermoplastic pommylunc [We ,lmimidm polyurethanes of this invention give lower viscosity Toluene diiwciwmw fill/3U isomers 334.8 3311.5 solutions with the highly polar solvents such as di- WWW), in MEKCW r, methyl formamide, dimethyl sulfone, or even dimethyl ketone.

The nature of this invention can be more readily understood by reference to the following exemplary EXAMPLE IV and illustrative examples where the parts or percent- These polyurethane compounds were prepflfgd i th ages are y Weight unless Othmwlse indicatedsame manner described in Example I using polyether EXAMPLEI recipes 4A and 48. They are similar except that an equimolar amount of DHE in B was substituted for Three hundred ninety-two parts of a poly caprolac- HEHQ i 4 f T bl IV; tone glycol of I200 molecular weight formed by initiat- TABLE [v ing the polymerization of E-caprolactone with diethyl- 4o cne glycol was degassed under vacuum at 90C. for l 43 hour in a reactor. Then 94.4 parts of di-(Z-hydroxp q r m thylcne lycol ylethyl) dimethyl hydantoin (sometimes called DHE). it-mun molecular weight 4uu 400 68.2 parts neopentyl glycol, sometimes called NPG. 22?, ig and 5.0 parts of 2-amin0-2-methyl propanol, some- 45 isied t-mo glycol (MP0) 2:? 2.7 times called AMP, were added to the reactor with stir- 332 5 J; 1 ring. The reactor temperature dropped to 80C. and o 320.5 11.13 3 [5.4 parts of isophorone diisocyanate, sometimes pmrlvrlifisl called lPDl, was added and stirred for 5 minutes. Mmmlu" l 3l)()% Modulus. psi 513 U5: The contents of the reactor were transferred to quart Ummm mug Psi 4373 mm cans and heated for 3 hours at 138C. and allowed to Ult t l s t Z2 cool to room temperature before being cut in pieces one-fourth inch to one-half inch size and dissolved in y sufficient solvent to give a 20 percent solution. The ml": hidmqmww m SOlVGnIS \Ncl'c methyl kfitone and dimeth *lsnmic is a code designation for ti commeminl toluene diisoeyimnle Mill" ylformamide (DMF). The solutions were cast into films on a polyethylene slab. Physical properties were determined on the solvent-free film and the results are EXAMPLE V Show" in Table The ingredients of Recipe 5A and 53 were mixed and TABLE reacted according to the prepolymer method to form a Pmpcmw cured polyurethane on standing overnight. The cured polyurethane had physical properties shown in Table 5 lUlWr Modulus, psi lllUS below; 3()(l'/r Modulus. psi 2895 l'ltimate Tensile. psi 5605 5 TABLE V lltimate Elongation. "r' 4l7 Viscosity Ill'u' MFK. cps 1 l4 5A 5B t Polytetramcthylene glycol of llltll) molecular eight 40 401) TABLE V-continued Dipropylenc glycol IDPG) I07 I07 DHE (i5 ('15 Ethylene glycol 3 l 3! [)iglycolarninc (l'XiA) 5.25 5.35 MD! 323.5 H,. .Ml)l 330.2 Reaction Ratio ()H/NCO 0.975 0.975 Properties: Viscosity in [)MF solution. cps 2020 3I70 Viscosity in 209 THF solution. cps H1380 I870 Short: A hardness 95 so Tensile. psi 7)h5 7018 1 Elongation. psi 363 K I005; Modulus. psi 7K5 i468 300 Modulus. psi 52x0 5065 The high hardness of these polyurethanes was unusual in that they were still soluble in DMF and THF. The solvent solutions of these polyurethanes are particularly desirable for spray coating objects and yield coated objects having a very tough polyurethane coating. Also. these polyurethanes in pelletized form can be fed to an extruder and used to cxtrude various shaped objects such as hose. grommets. sheet. boards and The reactive hydrogen material of 700 and higher molecular weight and preferably 1000 to 3000 molecular weight useful in this invention are well known and well described in U.S. Pat. No. 3,072,582 to Frost. Also. this patent discloses a list of representative examples of the organic polyisocyanates useful in this invention. Likewise. U.S. Pat. No. 3,036,996 to Kogan discloses the organic diamines useful as supplemental curatives and Frost discloses the monomeric polyols as precursors for preparation of the polyether polyols.

While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

What is claimed is:

l. A polyurethane prepared by reacting a mole of a reactive hydrogen material of 700 and higher molecular weight selected from the class consisting of polyester polyols and polyether polyols. with L2 to 3.5 moles of organic polyisocyanate and 0.2 to 2 moles of hydantoin containing dihydroxy alkyl and dialkyl substituents where the alkyl radical contains from 1 to l0 carbon atoms.

2. The polyurethane of claim 1 wherein the dihydroxy alkyl substituent is Z-hydroxyethyl and the dialkyl substituent is dimethyl.

3. The polyurethane of claim 1 wherein the polyisocyanate is selected from the class consisting of hydrogenated methylene di(phenyl isocyanate) and isophorone diisocyanate. 

1. A POLYURRETHANE PREPARED BY REACTING A MOLE OF A REACTIVE HYDROGEN MATERIAL OF 700 AND HIGHER MOLECULAR WEIGHT SELECTED FROM THE CLASS CONSISTING OF POLYESTER POLYOLS AND POLYETHER POLYOLS, WITH 1.2 TO 3.5 MOLES OF ORGANIC POLYISOCYANATE AND 0.2 TO 2 MOLES OF HYDANTOIN CONTAINING DIHYDROXY ALKYL AND DIALKYL SUBSTITUENTS WHERE THE ALKYL RADICAL CONTAINS FROM 1 TO 10 CARBON ATOMS.
 2. The polyurethane of claim 1 wherein the dihydroxy alkyl substituent is 2-hydroxyethyl and the dialkyl substituent is dimethyl.
 3. The polyurethane of claim 1 wherein the polyisocyanate is selected from the class consisting of hydrogenated methylene di(phenyl isocyanate) and isophorone diisocyanate. 